Process for preparing oxyalkylated derivatives



United States Patent 1 i ill-7V 7 2,854,447 PROCESS FOR PREPARING OXYALKYLATED DERIVATIVES Louis T. Monson, Puente, and Woodrow J. Dickson,

Monterey Park, Calif., assignors to Petrolite Corporation, Los Angeles, Calif., a corporation of Delaware No Drawing. Application June 4, 1953 Serial No. 359,663

8 Claims. (Cl. 260-232) This invention relates to the preparation of substantially anhydrous and substantially undiluted oxyalkylated derivatives of a particular class of oxyalkylation-susceptible organic compounds which, because of certain characteristics they possess, are not otherwise oxyalkylatable to produce such derivatives.

Oxyalkylation-susceptible organic compounds are characterized by their possession of labile hydrogen atoms, i. e., hydrogen atoms attached to oxygen, nitrogen, or sulfur. Their oxyalkylation may proceed with greater or lesser readiness; but oxyalkylated derivatives can be prepared from them.

The oxyalkylating agents conventionally employed to produce oxyalkylated derivatives are the lower alkylene oxides, ethylene oxide, propylene oxide, butylene oxide, glycid, and methylglycid. These may be defined as alphabeta alkylene oxides containing four carbon atoms or less. They may be employed singly, in sequence, or in admixture.

Unfortunately, there are some situations, like those with which this invention is concerned, in which the employment of such conventional oxyalkylating agents is not practicable. Some starting materials, although inherently oxyalkylation-susceptible, are solids which are substantially insoluble in any of the oxyalkylation-resistant solvents available for use in the preparation of oxyalkylated derivatives.

For example, many oxyalkylation-susceptible solids are insoluble in xylene, which is a frequently used solvent in oxyalkylation procedures. Xylene is oxyalkylationresistant and is readily separable from the oxyalkylation mass by simple distillation.

Furthermore, even though such starting materials may be soluble in a few unusual oxyalkylation-resistant solvents, the latter are themselves comparatively nonvolatile. Various ethers might in some cases be considered suitable solvents forthe oxyalkylation-susceptible solid starting material. Such ethers, like the diethers of the polyglycols, in addition to being expensive, are not susceptible to easy separation from the oxyalkylation mass by distillation. Hence, they are not readily recoverable from the oxyalkylation mass by distillation, to leave an undiluted oxyalkylated derivative.

Some solids which are oxyalkylation-susceptible are in fact most soluble in water; but Water is not an acceptable solvent for use in oxyalkylation processes employing the conventionally used alkylene oxides because it reacts with such alkylene oxides to produce polyglycols, during oxyalkylation.

We are aware that it has beenproposed in the past to conduct oxyalkylations using the conventional alkylene oxides in aqueous solutions, presumably on the assumption that the oxide did not react with the Water. However, it is now established that such reaction with the water occurs to some extent. The oxyalkylated mass produced in such aqueous systems therefore contains varying proportions of alkylene glycols as contaminants or adulterants. Our process avoids this difficulty because.

2. p it is conducted'underlsubstantially anhydrous conditions in all cases. Thestarting solid material, the catalyst, and the alkylene carbonates employed by us are all used in substantially anhydrous form.'

Furthermore, many oxyalkylation-susceptible solids cannot be used in undiluted form in an oxyalkylation process using the alkylene oxides, and simply liquefied by heating prior to introduction of the oxyalkylating agent,

because they undergo partial decomposition as they melt.

If maintained at the temperature at which fusion just begins to be apparent, for a time such as 15 minutes, they undergo at least partial decomposition. If they exhibit such behavior in the presence of an oxyalkylation catalyst, like the alkali carbonates, they come within our class of suitable starting materials for use in our present process.

The foregoing statementof difiiculties is applicable to greater or lesser extent to a number of oxyalkylationsusceptible compounds, including those recited below. The alkylene oxides are not usable for their oxyalkylation for the above stated reasons.

Our present invention overcomes such difficulties and permits oxyalkylation of such materials to be accomplished by simple and inexpensive means. Thus, we employ as primary oxyalkylating agents the carbonates which are the counterparts of the foregoing alkylene oxides, viz., ethylene carbonate, propylene carbonate, butylene carbonate, hydroxypropylene carbonate, and hydroxybutylene carbonate. Of these, only ethylene carbonate and propylene carbonate are currently in commercial production, although the others will doubtless achieve similar commercial status in time.

More specifically, our invention relates to a twostep process for preparing substantially anhydrous, substantially undiluted oxyalkylated derivatives from an anhydrous, solid, oxyalkylation-susceptible cellulosic compound, which solid satisfies one of the following two conditions: (a) it is infusible; (b) it suifers at least partial decomposition it maintained at its beginning-offusion temperature for a period of at least 15 minutes in the presence of an oxyalkylation catalyst, and which solid is insoluble in oxyalkylation-resistant, distillationseparable solvents; which process consists in:- (A) first reacting said solid with at least one alkylene carbonate selected from the class consisting of ethylene carbonate, propylene carbonate, butylene carbonate,'hydroxypropylene carbonate, and hydroxybutylene carbonate, in presence of an oxyalkylation catalyst; the proportion of alkylene carbonate employed being sufficient to yield a produce which is at least liquefiable at the temperature required to elfect its subsequent oxyalkylation using at least one alkylene oxide selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycid, and methylglycid; and (B) subsequently reacting such partially oxyalkylated derivative with at least one member selected from the aforesaid class of alkylene oxides.

Briefly described, our process is practiced by introducing into a suitable processing vessel the solid, oxyalkylation-susceptible starting material, preferably in finely divided form; the desired or required proportion of alkylene carbonate; and a minor proportion of an alkaline catalyst such as an alkali carbonate. The mixture is warmed, preferably with stirring. As the temperature reaches a certain critical level, usually somewhat above 0, there is a vigorous elfervescence in which carbon dioxide is liberated, and the oxyalkylated derivative is formed. In such instances where the starting material is acidic, it is used at least partially in the form of a salt, e. g., an alkali salt such as may be produced in situ by adding enough alkaline catalyst to leave a slight excess over what is required to leave the mixture slightly alkaline.

It is sometimes desirable to modify this general procedure in various minor ways. For example, the alkylene carbonate is introduced into a vessel and warmed until liquid. The catalyst is added. The solid, oxyalkylationsusceptible material is then slowly introduced in finely divided form, with stirring, and the temperature is slowly raised to the reaction point. Such procedural variation is useful where the oxyalkylation-susceptibility of the starting material is not great and where use of the firstdescribed procedure above would produce a solid mass in the vessel which could not be readily handled thereafter.

In'our process, we usually employ only enough alkylene carbonate in the first step to produce a liquid or readily liquefiable derivative, which contains a relatively small proportion of oxyalkylene radicals. We then continue oxyalkylation using the conventional alkylene oxides. Stated another way, this two-step process is employed to produce, first, intermediates; then more highly oxyalkylated products are prepared in the second step using the more economical, conventional alkylene oxides.

In the appended claims, we have specified that the intermediate product prepared in the first step of the two-step process shall be a liquid or at least liquefiable at the temperature required to effect the oxyalkylation by use of the alkylene oxides in the second step of our process. Said second step is conducted at conventional oxyalkylation temperatures, usually between about 100 C. and 200 C.

One incidental advantage of using the alkylene carbonates for oxyalkylation is that they are relatively inert materials as compared wtih the alkylene oxides. Their use therefore entails smaller hazards. Oxyalkylations using them are conducted with greater safety than if the alkylene oxides were employed. Processing vessels are usually not required to be pressure-resistant when the alkylene carbonates are employed, whereas ethylene oxide and propylene oxide, for example, are required to be employed in pressure vessels because of their physical properties.

All oxyalkylation-susceptible cellulosic compounds usable as starting materials do not react with equal readiness with the alkylene carbonates in our process. Where the starting material, although presumably oxyalkylationsusceptible as judged by its structure, is of very high molecular weight, or where steric or other obscure influences are adverse, oxyalkylation may proceed at extremely slow rates. However, if the starting material is oxyalkylationsusceptible, its oxyalkylation may be accomplished in due time by means of the alkylene carbonates mentioned above.

The temperature at which the oxyalkylation reaction will occur, using the alkylene carbonates, must be expected to vary somewhat with the choice of cellulosic starting material and alkylene carbonate. In all cases, the proper technique to be initially employed is to advance the temperature cautiously and so to determine the minimum temperature required to effect reaction. This procedure requires no especial skill and no experimentation, in that the vigorous efiervescence resulting from the liberation of carbon dioxide in the reaction is ready evidence of such reaction. As stated above, the reaction usually requires a temperature somewhat above 100 C. The maximum feasible oxyalkylation temperature is of course the decomposition temperature for the mixture of solid starting material, catalyst, and alkylene carbonate, and above which temperature pyrolysis of the starting material, polymerization of the alkylene carbonate, or other undesired reaction begins to occur.

The oxyalkylation catalysts employed by mere usually the alkali carbonates such as sodium or potassium car-- bonate, in substantially anhydrous form. Where the starting material is acidic, at least suflicient alkali carbonate should be addedto neutralize suchacidity. There- 4 after an additional amount of alkali carbonate is usually desirably included to accelerate the oxyalkylation process. However, in some instances the alkali-neutralized starting material is sufficiently alkaline to supply the desired catalytic influence, without addition of further amounts of alkali carbonate.

The finished oxyalkylated product will of course contain such inorganic catalyst. The catalyst will usually separate readily from the oxyalkylated mass on standing, especially if slightly warm. Since the residual proportions of catalyst in the supernatant product are usually of very small magnitude after such settling, we consider they do not materially dilute or contaminate our finishedproducts.

In some instances, solid, oxyalkylation-susceptible substances, which may have been stated in the literature to have definite melting points, are nevertheless susceptible to progressive decomposition if maintained at or about the temperature at which they begin to fuse, for any period of time. Some such substances similarly undergo progressive deterioration if subjected to such temperature in the presence of an alkaline material, like an oxyalkylation catalyst, for any period of time. Such substances which, although they may have recorded definite melting points, are unstable under oxyalkylating conditions as described, are included among our usable starting materials.

We have therefore limited our usable starting materials to those which are either (1) infusible or which (2) suffer at least partial decomposition if maintained at their beginning-of-fusion temperature for a period of at least 15 minutes in the presence of an oxyalkylation catalyst. Additionally, such solid starting material must be insoluble in oxyalkylation-resistant, distillation-separable solvents, as already stated.

As the molecular weight of the alkylene carbonate rises, its reactivity with the cellulosic starting materials is reduced. Since, for example, ethylene carbonate is more reactive than propylene carbonate, and propylene carbonate is more reactive than butylene carbonate, there may be marked difierences in the speed of oxyalkylation when different alkylene carbonates are used. In marginal cases, it will be understood, a cellulosic starting material may be oxyalkylation-susceptible in the sense that it is readily reactive toward ethylene carbonate or propylene carbonate, but it may be rather insensitive toward butylene carbonate.

Our process may be practiced using more than one alkylene carbonate, and in addition, more than one alkylene oxide, to produce mixed oxyalkylated derivatives. In such cases, the alkylene carbonates may be employed in sequence or they may be employed as a mixture, as desired. The same is true of the alkylene oxides employed in our two-step process, which may be used in sequence or as a mixture.

The oxyalkylation-susceptible starting materials embraced within our present class have been termed cellulosic, in the foregoing paragraphs. Cellulose itself is a carbohydrate, occurring in many plants. It is understood to contain three free hydroxyl groups for each six carbon atoms present in the molecule. These can be methylated, esterified, and, of course, oxyalkylated. It is therefore included here. Within our class of cellulosic starting materials, we also include such cellulose derivatives as bear a simple genetic relationship to the parent cellulose, and which retain their oxyalkylation-susceptibility.

We therefore include, for example, such cellulose derivatives as carboxymethylcellulose, carboxyethylcellulose, carboxypropylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose, in addition to cellulose itself. Cellulose derivatives which. areboth carboxyalkylated and. hydroxyalkylated, such as carboxymethylhydroxyethylcellulose, are also included.

Cellulose is of varying molecular weight. The highermolecular-weight celluloses are relatively inert to oxyalkylation except on long-continued reaction. We prefer to employ alkali cellulose as our cellulose starting material here. Alkali cellulose is a cellulose salt, resulting from the reaction of alkalies, such as sodium hydroxide, and cellulose. In its production, the esterified and free carboxyl groups present in the cellulose reactant are saponified and neutralized by the alkali. Alkali cellulose is produced from wood pulp and other cellulose stocks, and is used as a starting material for the production of viscose rayon.

As examples of our process, in which the foregoing starting materials are usable, the following are typical but not exclusive.

In all cases, the apparatus employed to produce the products in the laboratory was a conventional resin pot assembly, fitted with a stirrer. This is a glass apparatus comprising a lower bowl or vessel, and an upper cap section containing several outlets, for the stirrer shaft, a thermometer, and a reflux condenser, and a charge hole fitted with a stopper. The design is conventional and need not be described further. Heat is supplied by a glasstextile heating mantle which fits the lower portion of the assembly, and which is regulated by inclusion of a rheostat in the electrical circuit. Such devices are likewise wholly conventional, and require no description here. Motordriven stirrers, of the kind here used, and having stainlesssteel or glass shafts and paddles, are likewise conventional iaboratory equipment.

Example 1 Heat grams of commercial grade alkali cellulose with 352 grams of ethylene carbonate and 5 grams of powdered sodium carbonate in a conventional laboratory resin pot assembly, stirring the mixture, and increasing the temperature slowly over a period of about an hour, to about 195-200 C. Maintain this temperature, with stirring, for a total period of about 24 hours. An effervescence is observed, in which carbon dioxide is liberated. Theproduct is a dark, viscous liquid.

Example 2 We have repeated Example 1, but substituting for the alkali cellulose 10 grams of hydroxymethylcellulose. Otherwise, the procedure of Example 1 was followed. The product was a viscous, dark liquid.

Example 3 We have repeated Example 1, but substituting for the alkali cellulose 10 grams of hydroxyethylcellulose. The procedure was otherwise the same as in Example 1. The product was a viscous, dark liquid.

Example 4 We have repeated Example 1, but substituting for the alkali cellulose 10 grams of hydroxypropylcellulose. The procedure was otherwise the same as in Example 1. The product was a viscous, dark liquid.

Example 5 Heat 10 grams of commercial carboxymethylcellulose with 352 grams of ethylene carbonate and 5 grams of powdered sodium carbonate in a conventional laboratory resin pot assembly, stirring the mixture, and increasing the temperature slowly over a period of about 40 minutes, to about 195-200 C. Maintain this temperature, with stirring, for a total period of about 4 hours. An effervescence is observed, in which carbon dioxide is liberated. The product is a viscous, dark liquid.

Example 6 We have repeated Example 5, but substituting for the carboxymethylcellulose 10 grams of carboxyethylcellulose. The procedure was otherwise the same as in Example 5. The product was a viscous, dark liquid.

6 Example] We have repeated Example 5, but substituting for the carboxymethylcellulose 10 grams of carboxypropylcellulose. The procedure was otherwise the same as in Example 5, The product was a viscous, dark liquid.

Example 8 same as in Example 5.

Example 10 We have repeated Example 5, using carboxymethylcellulose. Then, after transferring the reaction mass to a conventional oxyalkylating autoclave, adding 5 grams of sodium hydroxide, and heating to 165 C., we have introduced into the mass, with stirring, 132 grams of ethylene oxide. The pressure did not exceed about 50 p. s. i.; and the procedure consumed about 2 hours. The product was a dark, viscous liquid.

V Example 11 We have repeated Example 10, except that we have substituted for the ethylene oxide there used 174 grams of propylene oxide, and have maintained the temperature during the second oxyalkylating step at about C. The second step consumed about 4 hours. The product was a dark, viscous liquid.

Example 12 We have repeated Example 10, but after introducing 132 grams of ethylene oxide, we have introduced 358 grams of propylene oxide. The time required to introduce this amount of propylene oxide was about 8 hours. The product was a dark, viscous mixture.

Example 13 We have repeated Example 5, using carboxymethylcellulose, but instead of using ethylene carbonate as the oxyalkylating agent we have substituted 348 grams of butylene carbonate. The product was a dark, viscous liquid.

Example 14 We have repeated Example 5, using carboxymethylcellulose, but instead of using ethylene carbonate as the oxyalkylating agent we have substituted 354 grams of hydroxypropylene carbonate. The product was a dark, viscous liquid.

Example 15 We have repeated Example 5, using carboxymethylcellulose, but instead of 'using ethylene carbonate as the oxyalkylating agent we have substituted 396 grams of hydroxybutylene carbonate. The product was a dark, viscous liquid.

Example 16 We have repeated Example 9 above. Then, after transferring the reaction mass to .a conventional oxyalkylating autoclave, adding 5 grams of sodium hydroxide, and heating to about C., we have introduced into the mass, with stirring, a mixture of 132 grams of ethylene oxide and 174 grams of propylene oxide. The second step consumed about 5 hours. The product was a viscous, dark liquid.

7 Example 17 We have repeated ExampleS, but substituting for the carboxymethylcellulose 10 grams of carboxymethylhydroxyethylcellulose. The proceduce was otherwise the same as in Example 5. The product was a viscous, dark liquid.

Example 18 We have repeated Example 5, but substituting for the carboxymethylcellulose 10 grams of commercial oxidized cellulose. The procedure was otherwise the same as in Example 5. The product was a viscous, dark liquid.

The products of our processes find a number of uses. They are surface-active, and hence are usable where lowsurface-tension solutions are useful, as in wetting, dispersing, and emulsifying operations. They are sometimes useful in demulsifying processes, in which water and oil are separated from their emulsions, and particularly crude oil and oil-field waters. Our oxyalkylated derivatives of the carboxyalkylcelluloses are useful as thickening agents for acidic solutions and as additives to oil-well drilling fluids. Our oxyalkylated derivatives of the hydroxyalkylcelluloses are useful in aiding the separation of oil from oil-bearing sands. Our oxyalkylated derivatives of the carboxyalkylhydroxyalkylcelluloses are useful in retarding the set'time of cements. ur oxyalkylated derivatives of oxidized cellulose-are useful in medicine as adsorbents.

We include among our'suitable cellulosic starting-materials those alkylcelluloses, such as methylcellulose and ethylcellulose, wherein the alkylation has been carried substantially short of completeness, so that they still retain a measure of oxyalkylation-susceptibility.

We claim:

1. A two-step process for preparing substantially anhydrous, substantially undiluted oxyalkylated derivatives from an anhydrous, solid, oxyalkylation-susceptible cellulosic compound, which solid satisfies one of the following two conditions: (a) it, is infusible; (b) it suffers at least partial decomposition if maintained at its beginning-of- 'fusion temperature for a periodof at least 15 minutes -'glycid,,and :methylglycid; and (B) subsequently reacting suchpartially oxyalkylated derivative with,at least one member selected'from the aforesaid class of alkylene oxides.

.2. ;.T he; process of claim 1, wherein the oxyalkylationsusceptible starting materialis alkali cellulose.

3. The processof claim 1, whereinthe oxyalkylationsusceptible starting material .is a carboxyalkylcellulose.

4. The process ofclaim 1, wherein the oxyalkylationsusceptible starting material is carboxymethylcellulose.

V .5. .The process of claim 1, wherein the oxyalkylationsusceptible starting material is carboxyethylcellulose.

6. .The process of claim 1, wherein the oxyalkylationsusceptible starting material is a hydroxyalkylcellulose.

7. The process of claim 1, wherein the oxyalkylationsusceptible starting material is hydroxymethylcellulose.

t8. T he'process. of-claim 1, wherein the oxyalkylationsusceptible starting material .is 'hydroxyethylcellulose.

-:Reierences ,Cited in thefile of, this patent UNITED STATES PATENTS I Carlson Sept. 7, 1948 OTHER. REFERENCES Schorger et al.: Industrial & Eng. Chemistry, vol. 29, No. 1, pages 114-117. 

1. A TWO-STEP PROCESS FOR PREPARING SUBSTANTIALLY ANHYDROUS, SUBSTANTIALLY UNDILUTED OXYALKYLATED DERIVATIVES FROM AN ANHYDROUS, SOLID, OXYALKYLATION SUSCEPTIBLE CELLULOSIC COMPOUND, WHICH SOLID SATISFIES ONE OF THE FOLLOWING TWO CONDITIONS: (A) IT IS INFUSIBLE; (B) IT SUFFERS AT LEAST PARTIAL DECOMPOSITION IF MAINTAINED AT ITS BEGINNING-OFFUSION TEMPERATURE FOR A PERIOD OF AT LEAST 15 MINUTES IN THE PRESENCE OF AN OXYALKYLATION CATALYST, AND WHICH SOLID IS INSOLUBLE IN OXYALKYLATION-RESISTANT, DISTILLATIONSEPARABLE SOLVENT; WHICH PROCESS CONSISTS IN (A) FIRST REACTING SAID SOLID WITH AT LEAST ONE ALKYLENE CARBONATE SELECTED FROM THE CLASS CONSISTING OF ETHYLENE CARBONATE, PROPYLENE CARBONATE, BUTYLENE CARBONATE, HYDROXYPROPYLENE CARBONATE, AND HYDROXYBUTYLENE CARBONATE, IN THE PRESENCE OF AN ALKALINE OXYALKYLATION CATALYST; THE PROPORTION OF ALKYLENE CARBONATE EMPLOYED BEING SUFFICIENT TO YIELD A PRODUCT WHICH IS LIQUID AT THE TEMPERATURE REQUIRED TO EFFECT ITS SUBSEQUENT OXYALKYLATION USING AT LEAST ONE ALKYLENE OXIDE SELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCID, AND METHYLGLYCID; AND (B) SUBSEQUENTLY REACTING SUCH PARTIALLY OXYALKYLATED DERIVATIVE WITH AT LEAST ONE MEMBER SELECTED FROM THE AFORESAID CLASS OF ALKYLENE OXIDES.
 3. THE PROCESS OF CLAIM 1, WHEREIN THE OXYALKYLATIONSUSCEPTIBLE STARTING MATERIAL IS A CARBOXYALKYLCELLULOSE. 